Plasma‐Assisted Coupling Reactions of Dinitrogen and Carbon Dioxide Mediated by Monometallic YB1–4−⋅Anions: Carbon−Nitrogen Bond Formation.

Transition‐metal catalyzed coupling to form C−N bonds is significant in chemical science. However, the inert nature of N2 and CO2 renders their coupling quite challenging. Herein, we report the activation of dinitrogen in the mild plasma atmosphere by the gas‐phase monometallic YB1–4− anions and further coupling of CO2 to form C−N bonds by using mass spectrometry and theoretical calculation. The observed product anions are NCNBO− and N(BO)2−, accompanied by the formation of neutral products YO and YB0–2NC, respectively. We can tune the reactivity and the type of products by manipulating the number of B atoms. The B atoms in YB1–4N2− act as electron donors in CO2 reduction reactions, and the carbon atom originating from CO2 serves as an electron reservoir. This is the first example of gas‐phase monometallic anions, which are capable to realize the functionalization of N2 with CO2 through C−N bond formation and N−N and C−O bond cleavage. [ABSTRACT FROM AUTHOR]